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 HYDROGEN: ITS TECHNOLOGY AND
IMPLICATIONS
E d ito rs

Kenneth E. Cox K. D. Williamson, Jr.

P ro je c t M an ag er
T h erm o ch em ical H y d ro g en
Los A lam os S cientific L a b o ra to ry
U niversity o f C a lifo rn ia
Los A lam o s, New M exico
A ssistan t D ivision L ead er
Los A lam o s Scientific L a b o ra to ry
U niversity o f C a lifo rn ia
Los A lam o s, New M exico

SERIES OUTLINE

Volume I
Hydrogen Production Technology
Volume II
Transmission and Storage of Hydrogen
Volume III
Hydrogen Properties
Volume IV
Utilization of Hydrogen
Volume V
Implications of Hydrogen Energy
 Hydrogen: Its
Technology
and
Implications
Volume II
Transmission and Storage
Editors:

Kenneth E. Cox K. D. Williamson, Jr.

Project Manager, Thermochemical Hydrogen Assistant Divison Leader
Los Alamos Scientific Laboratory Los Alamos Scientific Laborato1
University of California University of California
Los Alamos, New Mexico Los Alamos, New Mexico

Boca Raton London New York

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First published 1977 by CRC Press
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 PREFACE TO HYDROGEN: ITS TECHNOLOGY AND IMPLICATIONS

The United States, Western Europe, Japan, and several other countries are presently
faced with an energy shortage due largely to an imbalance of energy consumption over
fossil energy production. This problem was dramatized in October 1973 during the Arab
embargo on the shipment of oil to the United States and the resultant large increases in
the price of crude oil. This shortage in energy supply was then termed the “energy crisis.”
It was a clear demonstration of the nation’s dependence on imported petroleum and its
vulnerability on both political and economic grounds. It is clear that the above problems
would worsen in the future unless more attention and effort are directed toward
increasing domestic energy production from both depletable and nondepletable sources
and reducing energy consumption.
In the short-term, until the year 2000, coal and nuclear energy are expected to play
dominant roles in meeting the energy shortage despite the environmental restrictions that
hamper the production and consumption of high-sulfur coal and similar difficulties (siting
and radioactive waste disposal) that have slowed the development of nuclear energy. In
the long-term, beyond the year 2000, it is imperative that all forms of renewable energy
be developed. These include solar energy, in such forms as wind, ocean thermal gradients,
and biomass; geothermal energy; and fusion.
A major problem with several of the renewable energy sources is that they are
intermittent and their energy density is low; thus, there is a need for an energy carrier
that can act as both a storage and transportation medium to connect the energy source to
the energy consumer. Many of the renewable energy forms, together with coal and fission
exhibit their energy in the form of heat release. It is necessary to develop an energy
carrier, other than electricity, to supply the transportation sector as well as overcome the
problems of electrical storage.
Hydrogen, the lightest element, has been suggested as the energy carrier of the future.
In itself, it is not a primary energy source but rather serves as a medium through which a
primary energy source (such as nuclear or solar energy) can be stored, transmitted, and
utilized to fulfill our energy needs. There are several distinct advantages to the use of
hydrogen as an energy medium. It can be made from water, an inexhaustible resource. On
combustion, water is the main product; thus, hydrogen can be regarded as a clean,
nonpolluting fuel. Indications from current research efforts suggest that hydrogen may be
produced from high-temperature heat sources at an efficiency greater than that of
electrical generation, thereby making hydrogen a more economical energy source than
electricity. Technology has already been developed for storing hydrogen as a pressurized
gas, a cryogenic liquid, or in the form of a metal hydride. Systems for transporting
hydrogen as a gas or a liquid have been developed with liquid hydrogen playing a major
part in NASA’s putting a man on the moon. Finally, hydrogen is of value as a chemical
intermediate, being used in fertilizer manufacture, methanol synthesis, and petroleum
treatment. This area of hydrogen utilization represents 3% of today’s energy consumption
and is expected to grow by a factor of five by the year 2000. The above concept of using
hydrogen is termed the “hydrogen energy economy” and has been receiving an increasing
amount of attention from energy scientists and engineers in the United States and abroad.
This series in five volumes represents a serious attempt at providing information on all
aspects of hydrogen at the postgraduate and professional level. It discusses recent
developments in the science and technology of hydrogen production; hydrogen
transmission and storage; hydrogen utilization; and the social, legal, political, environ­
mental, and economic implications of hydrogen’s adoption as an energy medium.
Although there are several reports of selected studies on hydrogen as a fuel, this is the
first comprehensive reference book that covers a wide range of topics of notable interest
and timely importance.
Volume I of the series discusses such topics as hydrogen production from fossil fuels,
nuclear energy, and solar energy. Hydrogen production technology from water by
traditional methods such as water electrolysis and newer attempts to split water
thermochemically are included with details of current research efforts and future
directions.
Volume II provides detailed design information on systems necessary for the storage,
transfer, and transmission of gaseous and liquid hydrogen. Cost factors, technical aspects,
and models of hydrogen pipeline systems are included together with a discussion of
materials for hydrogen service. Metallic hydride gaseous storage systems for the utility
and transportation industry are covered in detail, and the design Dewars and liquid
hydrogen transfer systems are examined.
Volume III focuses on hydrogen’s properties and provides in one location all of the
hydrogen data measured and compiled by the National Bureau of Standards, Cryogenic
Division. The properties are individually discussed, and tables of data are provided. The
properties of slush hydrogen are also included.
Volume IV covers the present and future uses of hydrogen. Hydrogen has been
suggested as a prime candidate for both air and surface transportation. In the utility
industry, hydrogen systems for peak shaving promise to play an important future role.
Both present and future domestic and industrial applications of hydrogen are surveyed.
These include present uses in ammonia and methanol synthesis and future uses in the
direct hydrogasification of coal to synthetic natural gas. Important to all of these
applications are the safety considerations in the use of hydrogen to allow for public
acceptance of hydrogen’s role as an energy medium.
Volume V is primarily concerned with the nontechnical aspects of hydrogen.
Economics of hydrogen energy systems will play a major part in determining the time
frame for hydrogen’s adoption. Cost analyses of such systems with return on investment
considerations are surveyed from the point of view of production, transmission, and
storage of hydrogen. The environmental, political, social, and legal implications of new
secondary energy forms such as hydrogen are discussed with reference to governmental
energy policy, the social costs of energy production and use, and the public’s acceptance
of a hydrogen energy medium.
The unusually broad nature of hydrogen demands the expertise that could only be
provided by a wide authorship; thus, some of the authors are the original authorities in
their respective fields. Although the subject matter treated in each chapter is, in general,
the author’s research work and his critical review of the state-of-the-art, the authors have
had complete freedom in choosing the particular important areas to be emphasized. As a
result, some chapters treat the subject matter in more detail than others with a greater
emphasis on the engineering or design aspects of a particular system. Therefore, each
chapter possesses its own special feature and appealing points. Due to the limited space in
the series, the editors have encouraged each author to supply an extensive list of
references at the end of his chapter for the benefit of interested readers. Detailed author
and subject indexes have been provided at the end of each volume.
 The editors, while striving to avoid duplication, have allowed some degree of overlap in
certain of the chapters for the sake of continuity and allowing the reader to view a
particular topic from two or more points of view. Further volumes on the topic of
hydrogen are planned, and we wish to hear from our readers as to areas that might have
been neglected or deserve a special chapter on their own.
We would like to express our sincere thanks to these authors and the staff of CRC
Press, Inc. in particular Mrs. Gayle Tavens and Miss Sandy Pearlman, for their efforts in
making these volumes possible. Lastly, we would like to thank our wives, Patricia R. Cox
and Ruth S. Williamson, for their encouragement and help during the time it took to edit
these five volumes.

K. E. Cox
Albuquerque, New Mexico
K. D. Williamson, Jr.
Los Alamos, New Mexico
March 1975
 PREFACE TO VOLUME II:
TRANSMISSION AND STORAGE OF HYDROGEN

This volume of Hydrogen: Its Technology and Implications deals with transmission
and storage technology. In Chapter 1, Mr. G. Garth Leeth discusses the transmission of
gaseous hydrogen. Equations used by the industry are given and discussed for use in
calculation of power requirements and costs. It is concluded that costs for transmitting
gaseous hydrogen are on the order of 50% greater than for natural gas on an equal energy
basis. The chapter concludes with a discussion of pipeline safety and operating
experience.
Mr. James Reilly covers the subject of metal hydride storage media in Chapter 2. Metal
hydride chemistry lays the foundation for a discussion of specific metal hydride systems.
This is followed by an informative section on hydride applications, pointing up the
versatility of such systems as energy storage media. More on this subject is, of course,
given in Volume IV.
Chapter 3 covers the subject of liquid hydrogen storage and transmission and is written
by Dr. F. J. Edeskuty and myself. Most of the technology presented here was developed
from 1957 to the early 1970s as part of our space and nuclear rocket programs. It is a
technology which is well developed and readily applicable to today’s energy problems.
The final chapter in the volume is by Dr. Anthony Thompson and is on the subject of
materials for hydrogen service. In this chapter the subject of hydrogen embrittlement is
covered, along with all other aspects related to the proper choice of materials for use in
hydrogen systems.
It is our feeling that this volume covers its subject completely and authoritatively. The
editors would appreciate comments to make future editions more valuable to the reader.
It has been a pleasure working with all of the authors in this volume. Both they and we
hope and believe that hydrogen will find a major place in our future energy systems and
that these volumes will make getting there a bit easier.

K. D. Williamson, Jr.
Los Alamos, New Mexico
August 1976
 THE EDITORS
Kenneth E. Cox, Ph.D., is a Staff Member in the High-Temperature Chemistry
Group at the Los Alamos Scientific Laboratory, Los Alamos, New Mexico. He is
currently performing research in developing practical thermochemical cycles that pro­
duce hydrogen by water-splitting. In his previous position as Professor of Chemical
Engineering at the University of New Mexico, Albuquerque, he pioneered the devel­
opment of photovoltaic-electrolytic methods to produce hydrogen from solar energy
and water.
Dr. Cox graduated in 1956 from the Imperial College of Science and Technology of
the University of London with B.Sc. and A.C.G.I. degrees in chemical engineering.
He received his M.A.Sc. from the University of British Columbia in 1959 and his
Ph.D. from Montana State University in 1962, also in chemical engineering.
Dr. Cox is a member of the American Institute of Chemical Engineers, the American
Chemical Society, and Sigma Xi, the Scientific Research Society. He is also a member
of the International Association for Hydrogen Energy and has contributed both as an
author and reviewer to the International Journal of Hydrogen Energy.
Dr. Cox has published numerous research papers and has given over 100 presenta­
tions. His current research interests include: thermochemical generation of hydrogen
from water, use of solar energy for hydrogen generation, techno-economic energy eval­
uations as well as traditional chemical engineering, e.g., thermodynamics of separation
processes, process design, and dispersion phenomena in fluids.
K. D. Williamson Jr., Ph.D. is Assistant Division Leader of the Systems Analysis
and Assessment Division, Los Alamos Scientific Laboratory, Los Alamos, New Mex­
ico.
Dr. Williamson received his B.S., M.S., and Ph.D. degrees in chemical engineering
from Pennsylvania State University in 1957, 1959, and 1961, respectively.
Dr. Williamson is a member and lecturer for the New Mexico Academy of Sciences
and has served as an invited lecturer at the University of Tennessee and New Mexico
Highlands University.
Dr. Williamson has published more than 35 research papers. His current interests
include technology assessments and systems analyses of energy-related topics in sup­
port of research and development decision makers at Los Alamos and the State and
National government levels.
 CONTRIBUTORS

F. J. Edeskuty J. J. Reilly
Associate Group Leader Chemist
Cryogenics Group Department of Applied Science
Los Alamos Scientific Laboratory Brookhaven National Laboratory
Los Alamos, New Mexico Upton, New York

Anthony W. Thompson
G. Garth Leeth Professor, Department of Metallurgy
Member of Professional Staff and Material Sciences
General Electric Tempo Carnegie Mellon Institute
Santa Barbara, California Pittsburg, Pennsylvania

K. D. Williamson, Jr.
Assistant Division Leader
Systems Analysis and Assessment
Division
Los Alamos Scientific Laboratory
Los Alamos, New Mexico
 TABLE OF CONTENTS

Chapter 1
Transmission of Gaseous Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
G. G. Leeth

Chapter 2
Metal Hydrides as Hydrogen Storage Media and Their Applications . . . . . . . . . . . . . . . . . . . . . . . . . 13
J. J. Reilly

Chapter 3
Liquid Hydrogen Storage and Transmission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
F. J. Edeskuty and K. D. Williamson, Jr.

Chapter 4
Materials for Hydrogen Service . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
A. W. Thompson

Unit Conversions, Physical Constants, and Symbols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
 Chapter 1
Transmission o f Gaseous Hydrogen
 Chapter 1
TRANSMISSION OF GASEOUS HYDROGEN

G. G. Leeth

TABLE OF CONTENTS

1.1. In tro d u c tio n ..................................................................................................................................... 3

1.2. Gas P ip e lin e s..................................................................................................................................... 3

1.3. Gas Pipeline D y n am ics..................................................................................................................... 4

1.4. Gas Pipeline Costs ......................................................................................................................... 3

1.5. Hydrogen Pipeline Analyses ......................................................................................................... 5

1.6. Hydrogen Pipeline Safety ............................................................................................................. 7

1.7. Hydrogen Pipeline Operating E x p e rie n c e ..................................................................................... 8

1.8. Conclusions ..................................................................................................................................... 9

R e fe re n c e s ........................................................................................................................................................ 10

1.1. INTRODUCTION material resource limitations. The “energy crisis”

has also spurred continued interest in hydrogen
During the late 1960s, a major interest in the development.
use of hydrogen arose in the scientific and For any hydrogen energy system, pipeline
engineering world community. This interest de­ transport of gaseous hydrogen is clearly a major
veloped due to the realization that hydrogen element. This chapter summarizes the present
possessed many characteristics of the ideal energy status of hydrogen pipeline knowledge. Technical
vector: aspects, cost features, safety considerations, and
operating experience are discussed.
1. It can be produced from water, an inex­
pensive and plentiful material. When burned, it 1.2. GAS PIPELINES
reverts to water, resulting in a cyclic process which
consumes energy but not raw materials. Bulk transmission of gases is routinely ac­
2. It is a gas under normal conditions and complished using pipelines. Approximately 30% of
should permit an easy transition from present the U.S. energy use in the form of natural gas is
natural gas and petroleum-fueled energy systems. moved in a pipeline network. Therefore, it is most
convenient to compare hydrogen pipelines with
Developmental activities in hydrogen energy existing natural gas pipelines.
systems have continued in the 1970s. These have In this chapter, the flow of gas in a pipeline is
been aided by environmental interests in clean described in terms of equations based on gas
fuels and conservationists’ concerns related to properties. Cost relationships are described basi-

3
cally in terms of pipe size and pumping power
requirements. A pipeline design and the cost ( 1. 2)
for a specified energy flow must be calculated.
By iteration, a minimum cost design can be
determined.
The most difficult relationships to obtain and (1.3)
validate are the costing algorithms. There are two
major reasons for this difficulty. First, actual
pipeline system costs depend strongly on terrain
(1.4)
difficulty and other factors associated with geo­
graphy. Second, all real pipelines are not opti­
mized for a specific flow, but are designed to
permit capacity increases by addition of more (1.5)
and/or larger compressors.
In general, calculations based on an optimum
(minimum cost) pipeline system appear to be ( 1.6)
satisfactory for comparison between gases under
varying conditions. The gas flow relationships are
correct, but the costing algorithms are true only
where Q = energy flow (MMBTU [million British
for some nominal conditions. Consequently, re­
thermal units] /hr); m = mass flow rate (slugs/sec);
lative comparisons are meaningful, but absolute
g = gravitational acceleration (32.2 ft/sec2); LHV
costs should be carefully evaluated.
= lower heating value of gas (Btu/lb); L = pipe
length between compressor stations (ft); D = inside
1.3. GAS PIPELINE DYNAMICS
diameter of pipe (ft); f = pipe friction factor; Pi =
initial gas pressure (lb/in.2); P2 = gas pressure at
Isothermal flow of a compressible fluid is used
length, L (lb/in.2); Mi = initial Mach number; k =
as a basis for practically all pipeline analyses by
ratio of gas specific heats; hp = compressor
the gas industry. Various formulations have been
horsepower; 17x = compressor efficiency; R = gas
devised to simplify calculations or answer specific
constant, T = temperature of gas (°R); Z = gas
questions. The parameters of interest usually
compressibility factor; p = gas density (slugs/
include energy flow, pipe diameter, distance be­
ft3); Re = - (Reynold’s number); e = pipe
tween compressor stations, pressure ratio, and
roughness parameter (typical value = 0.00015); t =
compressor horsepower. 0.7 P, • 12 *D _ .
Two recent analyses of hydrogen pipelines1’2 • = pipe thickness (in.).
6 0 ,0 0 0
use somewhat different formulations of the gas
It is assumed that the equations listed above
flow equations. Reference 2 also uses European
would be solved with a computer, and therefore,
cost data. The general conclusions of both refer­
simplicity is not a critical issue. If desired, several
ences are the same, although detailed comparisons
simplifications are possible. For example, temper­
are difficult. Results of the two methods of
ature, pressure, and Reynold’s number are nearly
calculation are shown in Section 1.5. A brief
constant for typical pipelines. Thus, the friction
description of the procedure followed in Refer­
factor becomes only a function of the roughness
ence 1 is given in the following pages as it is
parameter, and the rather complex definition given
probably more useful to American readers.
in Equation 1.6 is not needed.
Equations 1.1 to 1.3 describe the gas flow
relationships in terms of the parameters previously Equations 1.1 to 1.6 can be used in a variety of
mentioned. Equations 1.4 to 1.6 provide the ways. One method is to specify energy flow rate
additional relationships needed to solve the set of (Q), temperature (T), initial pressure (P j), pressure
Equations 1.1 to 1.3. All of the information in drop between compressors (Px - P2), and pipe dia­
these equations is fairly standard fluid dynamics. meter (D). Using these as inputs, the pipe length
For further details, see References 3 and 4. (L) and associated compressor power (hp) can be
calculated. Thus, a pipeline design can be defined
in terms of size and power requirements as a func­
( 1. 1)
tion of energy flow rate for various gas conditions.

4 Hydrogen: Its Technology and Implications

 1.4. GAS PIPELINE COSTS
Gas pipeline system costs are calculated using
Equations 1.7 to 1.11. Capital costs are calculated
from Equations 1.7 to 1.9 and fuel costs from
Equation 1.10. The inflation factors in Equations
1.7 and 1.9 are used to adjust cost data from
different years, when necessary. The total cost of
transporting gas per MMBTU per 100 mi is
calculated from Equation 1.11.
Cp = C1(A 1Wp + B112D + CR) (1.7)
Wp = 28.2 t (12D - t) (1.8)
Cc = C2(E ,-h p + F , 1 2 D ) ^ ^ (1.9)
where Cp = pipe capital cost ($/mi); Q and C2 =
inflation factors; Wp = weight of pipe (tons/mi);
Ai = specific cost of pipe ($/ton); Bi = instal­
lation cost ($/in.-mi); CR = right of way cost
($/mi); Cc = pumping station capital cost ($); Ei =
specific pumping cost ($/hp), compressor and
prime mover; Fi = pumping station cost ($/in. of
pipe diameter).
( 1. 1 0)
where CF = transport fuel cost ($/10 6 Btu-100
mi); hp = horsepower calculated from flow equa­
tions; Gi = fuel cost ($ / 106 Btu);r?2 = conversion
efficiency fuel to shaft power; Q = energy flow
rate of pipe (MMBTU/hr); L = distance between
compressor stations calculated from flow equa­
tions.
( 1. 11)
where CT = total cost of gas transport ($/10 6
Btu-100 mi); FCR = fixed charge rate; CF =
capacity factor of pipeline system.
1.5. HYDROGEN PIPELINE ANALYSES
Some numerical calculations were performed
using Equations 1.1 to 1.11 and empirical
constants as listed in Table 1.1. The results of
these computer analyses are summarized in Figures
1.1 to 1.4. The main source of the cost data
itemized in Table 1.1 was written in 1965.5
However, the use of these data resulted in excel-
TABLE 1.1
Numerical Constants
P, 1000 psi
17, 0.85
A, $200/ton
B, $1300/in.-mi
CR $6000/mi
E, $200/hp
F, $15,000/in. of pipe diameter
G, $0.40/106 Btu
0.40
FCR 0.15
CF 0.90
lent agreement with a proposed 36-in. Texas to
California natural gas pipeline.6 Accordingly, the
tabulated data are believed to be sufficiently
accurate for comparative analyses. .
The curves in Figures 1.1 to 1.4 are all
minimum cost systems. Operation and mainte­
nance costs are not included, but would have an
almost insignificant effect on comparisons. Figure
1.1 shows that for the same energy flow, hydrogen
costs approximately 1.4 times as much to
transport as natural gas. As noted previously, the
absolute costs are reasonably correct for transport
in the early 1970s in the southwestern U.S. With
current fuel prices and fabrication costs, gas
transportation costs in mid 1976 would be approx­
imately 50% higher than indicated in Figure 1.1.
Figures 1.2 and 1.3 summarize pipe size and
compressor power requirements for a range of
energy flows. Pipeline capital costs for two kinds
of terrain are shown in Figure 1.4. The lower
curves are typical of the southwestern U.S. and the
upper curve of more difficult terrain, such as
Alaska. Pipeline capital costs for most future
installations in the conterminous U.S. are likely to
fall between these two curves, closer to the upper
one.
In addition to the General Electric (GE) calcu­
lations summarized in Figures 1.1 to 1.4, two
other analyses of hydrogen pipelines have been
reported .2’7 Table 1.2 summarizes the conclusions
from three studies: GE ,1 EURATOM,2 and the
Institute of Gas Technology (IGT).7
The IGT computations assume that electrolytic
hydrogen is used to drive the pipeline compressors.
This results in a fuel cost five to ten times higher
than assumed by the GE and EURATOM studies,
and which explains the higher transmission cost
calculated by IGT. The slight differences in hy-
5
 FIGURE 1.1. Total pipeline transportation cost vs. energy flow.

FIGURE 1.2. Pipeline diameter vs. energy flow.

TABLE 1.2 The effect on compressor power of varying

flow through the pipe is shown in Figure 1.5.
C o m p arativ e T ransm ission C osts
Compression ratio variation affects both com­
GE EURATOM IGT pressor horsepower and cost. For natural gas, the
minimum cost occurs at a ratio of 1.25 to 1.30,
Natural gas 1.0 1.0 1.0 which is roughly the ratio currently used. The
Hydrogen 1.3-1.5 1-4—1.6 2 .0 -3 .0 corresponding pressure ratio for hydrogen is about
1. 1 , which corresponds to station spacings of 50
to 75 mi. The installed horsepower per mile is
drogen transmission costs as reported by GE and nearly constant for natural gas over a pressure
EURATOM are probably due to the cost data ratio range from 1.1 to 1.5.
used. With fuel costs at S0.40/MMBTU, capital costs

6 Hydrogen: Its Technology and Implications

 FIGURE 1.3. Pipeline compressor power vs. energy flow.
account for about 90% of total transmission costs.
At current fuel costs (on the order of
S2.00/MMBTU), it is estimated that the systems
would optimize at a capital cost equal to about
80% of total cost. The relative transmission costs
of hydrogen and natural gas are not significantly
affected by higher pumping energy costs, as long
as the same costs apply to both fluids.
In general, hydrogen transmission costs about
1.5 times as much as natural gas, where the
pumping energy costs are the same. Hydrogen also
requires about 1.5 times the pumping power of
natural gas. For a minimum cost hydrogen pipeline
at 10 10 Btu/hr, about 0.5% of the energy flow is
required for pumping, compared to approximately
0.35% for natural gas. As the energy flow in the
pipe or the pumping cost increases, the fraction of
energy used for pumping decreases.
1.6 HYDROGEN PIPELINE SAFETY
The major hazard associated with pipeline
transmission of hydrogen gas is leakage, followed
by combustion. Due to its small molecular size,
hydrogen is more likely to leak than any other gas.
Flammability limits are unusually large (4 to 75%
by volume with air) at normal temperature and
pressure. The ignition temperature (1075°F) is
higher than that of most hydrocarbons (400° to
700°F), but its ignition energy is an order of
magnitude lower. Once ignited, flame speeds are of
the order of tens of feet per second.
Hydrogen flames are nearly invisible and char­
acterized by a low level of radiation to sur­
rounding regions. Thus, a hydrogen fire is less
likely than a hydrocarbon fire to ignite other
combustible materials by radiation. However, since
a hydrogen flame is nearly invisible, it is difficult
to detect, making it more of a personnel hazard
than are hydrocarbon flames.
An explosion of hydrogen-air mixtures is very
unlikely to occur as a result of a pipeline leak.
Detonation limits of hydrogen-air mixtures range
from 18 to 59% by volume. Since the hydrogen
molecule has a very low mass, it would rise rapidly
in air. Unless the leak occurred in a confined
region, it is improbable that a concentration of
18% would be reached. Furthermore, the ignition
7
 FIGURE 1.4. Pipeline capital cost vs. energy flow.
energy for detonation is very large compared to
that required for combustion.
Hydrogen embrittlement is a potential concern
in a pipeline operation with hydrogen gas. Con­
siderable controversy exists as to the exact
mechanisms involved in such embrittlement (see
Chapter 4). It is clear that the degree of embrittle­
ment is dependent upon such parameters as the
type of alloy, operating stress level, impurities in
the hydrogen, and probably others not yet recog­
nized.
Almost all of the observed hydrogen embrittle­
ment has involved very pure hydrogen. Failures
resulting from embrittlement have usually been
associated with welds, rather than the base metal.
Small amounts of oxygen, carbon monoxide, and
other gases are effective in inhibiting hydrogen
embrittlement. Such impurities would be quite
acceptable for almost all energy or industrial uses
of hydrogen. It seems likely that a properly
8 Hydrogen: Its Technology and Implications
constructed hydrogen gas pipeline operating with
trace amounts of impurities should have no
embrittlement problems.
The use of existing natural gas pipelines to
transport hydrogen has often been suggested.
While this is probably feasible, the compatibility
of hydrogen with the specific pipeline would have
to be demonstrated. The problem is that welds,
valves, and pump components might suffer
hydrogen embrittlement and significant hydrogen
leakage might occur.
1.7 HYDROGEN PIPELINE
OPERATING EXPERIENCE
In the U.S., an 8-in. hydrogen pipeline has been
operating for several years from Bayport to
Baytown, Texas. Very little information about this
pipeline appears in the literature. Most of the
reported hydrogen pipeline operating experience is
 FIGURE 1.5. Effect on compressor power of off-optimum operation.
from Germany.12 A hydrogen pipeline network
208 km in length is in use in the Rhine-Rhur area.
The original segments of this network have been
operating since 1938. Pipe size varies, but much of
the system appears to be 300 mm in diameter.
Maximum pressure is 15-bar gauge; in 1973 the
integrated network handled some 206 million
standard cubic meters of hydrogen.
German operating experience, covering a period
of 30 years, has been quite good. Some fires have
occurred, but there have been no explosions or
any problems with hydrogen embrittlement.
Chemische Werke Hiils AG, the German operating
organization, has expressed a high degree of
confidence in their technical ability to design,
construct, and operate an integrated hydrogen
pipeline network.
1.8 CONCLUSIONS
Transmission of hydrogen gas in a large pipeline
network is technically and economically feasible.
For large energy flow rates, the transmisison cost
would be approximately 50% greater per energy
unit than for natural gas. Sufficient experience is
available to be confident that hydrogen pipelines
can be designed, built, and safely operated on a
commercially profitable basis. Modification of
existing natural gas pipelines to transport hy­
drogen is probably feasible.
9
 REFERENCES
1. Reynolds, R. A. and Stager, W. L., Transportation and Storage o f Hydrogen for Eco-Energy, Report GE72TMP-54,
General Electric-TEMPO, Santa Barbara, Calif., 1972.
2. Beghi, G., Ciborra, M., Dejace, J., and Massaro, C., Hydrogen, Oxygen and Natural Gas by Pipelines: Comparative
Transport Costs, Report EUR-5103.e, EURATOM-C.C.R., Ispra, Italy, 1973.
3. Shapiro, A. H., The Dynamics and Thermodynamics o f Compressible Fluid Flow, Ronald Press, New York, 1953.
4. Schlichting, H., Boundary-Layer Theory, McGraw-Hill, New York, 1968.
5. Khan, A. R. and Panos, P. S., The Economics o f Natural Gas Production, Transportation, Storage, and Distribution,
Institute of Technology, Chicago, 1965.
6. O’Donnell, J. P., Pipe installation and equipment costs, Oil GasJ., 61(27), 105, 1963.
7. Gregory, D. P. and Gillis, J. C., Survey o f Hydrogen Production and Utilization Techniques, Institute o f Gas
Technology, Chicago, 1965.
8. Swisher, J. H., Keaton, S. C., West, A. J., and Jones, A. T., Survey o f Hydrogen Compatibility Problems in Energy
Storage and Energy Transmission Applications, Energy Report SAND74-8219, Sandia Laboratories, Albuquerque,
N. Mex. and Livermore, Calif., 1974.
9. Parrish, W. R., Voth, R. O., Hust, J. G., Flynn, T. M., Sindt, C. F., and OJien, N. A., in Selected Topics on Hydrogen
Fuel, Hord, J., Ed., Report NBSIR 75-803, Institute for Basic Standards-National Bureau of Standards, Boulder,
Colo., 1975.
10. Kelley, J. H., and Laumann, E. A., Hydrogen Tomorrow: Demands & Technology Requirements, Jet Propulsion
Laboratory Report JPL 5040-1, Report of the NASA Hydrogen Energy Systems Technology Study, Pasadena,
1975.
11. Bowen, T. L., Investigation o f Hazards Associated with Using Hydrogen as a Military Fuel, Report 4541, Naval Ship
Research and Development Center, Bethesda, Md. 1975.
12. Isting, C., Experience with a Hydrogen Pipline Network, Chemische Werke Hiils AG (CWH), Federal Republic of
Germany, 1974.
13. Nelson, G. A., When to use low alloy steel for hydrogen service, Hydrogen Process., p. 45, 1966.

10 Hydrogen: Its Technology and Implications

 Chapter 2
M etal Hydrides as Hydrogen Storage
Media and Their Applications
 Chapter 2
METAL HYDRIDES AS HYDROGEN STORAGE MEDIA
AND THEIR APPLICATIONS

J. J. Reilly

TABLE OF CONTENTS

2.1. Introduction ....................................................................................................................................13

2.2. Metal HydrideC h e m is try ....................................................................................................................... 14

2.3. Specific Metal-hydrogenSystems and their P r o p e r tie s .......................................................................18

2.3.1. E x p e rim e n ta l..........................................................................................................................18
2.3.2. Magnesium and Magnesium Alloys ..................................................................................... 18
2.3.3. Rare Earth Alloys ................................................................................................................. 20
2.3.4. Iron-titanium A l l o y s ............................................................................................................. 26
2.3.5. Vanadium D ih y d rid e ............................................................................................................. 31

2.4. Applications ................................................................................................................................... 31

2.4.1. C rite ria ..................................................................................................................................... 31
2.4.2. Peak Shaving ......................................................................................................................... 35
2.4.3. A u to m o tiv e .............................. 37
2.4.4. Thermal Storage and Solar Energy ..................................................................................... 43
2.4.5. Pumps and Compressors ..................................................................................................... 44
2.4.6. S a f e t y ..................................................................................................................................... 45

A ck n o w led g m en t............................................................................................................................................. 46

R e fe re n c e s......................................................................................................................................................... 47

2.1. INTRODUCTION which limits such use is the difficulty involved in

sto rin g it conveniently and economically.
Hydrogen may be considered an ideal fuel for Currently, hydrogen may be stored as a com­
many reasons. It can be used in a variety of energy pressed gas or as a cryogenic liquid. Neither
converters ranging from fuel cells to internal method appears to be practical for many appli­
combustion engines. It is essentially nonpolluting cations in which hydrogen use would otherwise be
and can be made from readily available and attractive. For example, gaseous storage of hydro­
abundant raw materials and energy sources. In the gen for use as a common mobile or stationary fuel
near future, hydrogen could be produced relatively is not feasible because of the large volume and/or
cheaply from coal; in the more distant future, weight of the storage vessels. Liquid hydrogen
when fossil fuel reserves are exhausted, hydrogen could be used extensively as an aircraft fuel, but
could serve as a portable, storable fuel, produced would present difficult problems in more
by the electrolysis of water using electricity mundane, everyday applications. Furthermore, the
derived from a primary energy source (e.g., liquefaction process is relatively expensive and
nuclear, solar, or geothermal).1 requires about 5 kWh of electricity to liquefy 1 lb
Unfortunately, despite its unique attributes, of hydrogen. This amount of energy is an appreci­
hydrogen has not yet been widely exploited for able fraction of the combustion heat of hydrogen;
use as a fuel. Perhaps the most important factor when conversion efficiencies are taken into

13
 TABLE 2.1 review of this subject should refer to the works of
Libowitz,2’3 Mueller et al.,4 Fast,5 and Mackay.6
Properties of Representative Binary Metal Hydrides
Metal hydride compounds may be divided into
Hydride Wt % H Heat of formation (kcal) three general categories: saline or ionic, metallic,
%
and covalent. The classification is based on the
LiH 12.7 5.9 -21.7 predominant character of the hydrogen bond and
A1H3 10.1 - -2.7 is somewhat equivocal since no one compound
CaH2 4.2 5.1 -41.7
exhibits purely one type of bonding.
MgH2 7.6 6.6 -18
NaH 4.8 5.1 -13.6 In the ionic hydrides, the crystal lattice consists
TiH2 4.0 9.1 -3 0 of metal cations and hydrogen anions. Such
ZrH2 2.2 7.3 -39.7 hydrides are formed by the direct reaction of
LaH2 2.1 6.8 -49.7 hydrogen with the alkali and alkaline earth metals
uh3 1.3 8.4 -30.8
and magnesium, although the bonding of the latter
H2 Liquid 100 4.2 —
hydride exhibits an appreciable amount of co­
valent character. Hydrides of these metals are
Note: N h X 1022 = number of H atoms per cubic quite similar to their halide analogues both in
centimeter. structure and properties; the alkali metal hydrides
have the sodium chloride structure, while those of
account, it would require the expenditure of about the alkaline earths have a structure similar to that
1 lb of hydrogen fuel for every pound of liquid of barium chloride. With the exception of mag­
hydrogen produced. In view of this, any novel nesium, the ionic hydrides are too stable to be
hydrogen storage method that would make its use considered attractive hydrogen storage media.
as a common fuel feasible should be fully ex­ The metallic hydrides exhibit typical metallic
plored. properties having a metallic appearance and high
One potentially attractive alternative to conven­ thermal and electrical conductivities. They are
tional storage methods is storage as a metal formed by the reaction (usually direct) of hydro­
hydride. Such compounds are of interest because gen with most of the transition metals (periodic
of their high hydrogen density per unit volume, table Groups IIIA to VIIIA), including the
which (as noted in Table 2.1) may be substantially lanthanide and actinide series. Some metals (such
greater than that of liquid hydrogen. Unfortu­ as Zr or the monohydrides of V, Nb, and Ta) can
nately, when the same comparison is made on a be almost completely hydrided and still retain
weight basis, the hydrides are at a considerable their original shape and form; in others, such as U,
disadvantage because of the weight of the associ­ the hydride product is a very fine powder. Certain
ated metal. Therefore, the present use of such transition metal hydrides are prime examples of
materials has focused on stationary applications. the tendency of this type of compound to deviate
Nevertheless, hydrides cannot be discounted as from stoichiometry by very large amounts. There
mobile fuel sources, as has been recently demon­ is considerable uncertainty at present surrounding
strated.43,4 4 the state of the hydrogen atom and the nature of
The purpose of this chapter is several fold: to the bonding in metallic hydrides. Currently, there
acquaint the reader with the more salient and are three models (none of which is completely
pertinent aspects of metal hydride chemistry and satisfactory) which attempt to account for their
to delineate the properties of several individual observed properties. They are the proton model, in
metal-hydrogen systems of interest and discuss which the hydrogen is assumed to donate its single
their applications, particularly as energy storage electron to the d-band of the metal, thus existing
media. in the metal lattice as a proton; the covalent
model, where it is suggested that the bonding is
2.2. METAL HYDRIDE CHEMISTRY predominantly the electron sharing type; and the
anionic model, which is essentially the inverse of
In order to appreciate the potential of metal the proton model. In the latter case, the metal
hydrides as energy (hydrogen) storage media, a donates electrons to the hydrogen atom, which
general knowledge of their chemistry is required. consequently exists in the lattice as an anion. For
Those who are interested in a detailed account and14 a detailed discussion of these models (which is

14 Hydrogen: Its Technology and Implications

beyond the scope of this chapter), the reader is
referred to the citations previously noted.2"6
The covalent hydrides are formed by Be and
many of the B group metals of the periodic table.
These hydrides can be solid, liquid, or gaseous and
may be quite unstable. In certain cases, they are
quite toxic and readily take fire in air. Those
which are solid form polymers (e.g., BeH2, A1H3).
None of the covalent hydrides can be formed by
the direct reaction of the solid metal with hydro­
gen, except under special conditions; this ef­
fectively eliminates these materials from consider­
ation as practical hydrogen storage media.
The elements which form solid binary metal
hydrides by reacting directly with hydrogen are
shown in Figure 2.1. At this point, it may be
worthwhile to note that, despite the large number
of binary metal hydrides which exist, only two are
of any interest from an energy storage point of
view (i.e., magnesium hydride [MgH2] and
vanadium dihydride [VH2 ]). In its simplest form,
the equation for the formation of these
compounds may be written as follows:
M + (x -r 2)Ha « = > M H X (2.1)
Such a direct reaction is usually quite exothermic;
as noted in Table 2.1, the heat of formation of
several hydrides approaches that of the heat of
combustion of hydrogen. The reaction is reversi­
ble, and its direction depends on the hydrogen
pressure in the system.
The behavior of a metal-hydrogen system is
commonly and most conveniently represented by
a pressure, composition, temperature diagram. An
idealized diagram of this type, which can be
regarded as a special type of phase diagram, is
shown in Figure 2.2. It consists of a family of
isotherms which shows the variation of the equi­
librium pressure with the concentration of hydro­
gen in the solid. At a given temperature, hydrogen
will dissolve in the metal phase as the pressure
increases. This single-phase region is usually
designated as the a phase of the hydrogen-metal
system. Ideally, the isotherm in any single solid-
phase region will obey Sievert’s law, which states
that the concentration of hydrogen in the solid
phase is proportional to the square root of the
equilibrium pressure, P.
Conc- Hsolid = K p ,/l (2-2)
The fact that the equilibrium pressure appears in
the equation to the one half power indicates that
hydrogen dissociates on the metal surface and
dissolves in the metal as the hydrogen atom. Point
A in the isotherm marks the terminal solubility of
hydrogen in the a phase and also the appearance
of a distinct metal hydride or 0 phase. The
solubility of hydrogen in many metals can be
appreciable; thus, many metal hydrides are quite
nonstoichiometric. This is particularly true of
those metal hydrides with metallic bonding. Upon
the appearance of a second solid phase, the
hydrogen pressure remains constant and forms a
“plateau” as more hydrogen is added. However, it
should be noted that the concentration of hydro­
gen in each phase does not change as hydrogen is
added to the system; only the relative amounts of
each phase change. The pressure plateau persists as
long as two distinct solid phases coexist and is a
consequence of Gibbs phase rule. This states that
for a given system:
F = C- P + 2 (2.3)
where F = the degrees of freedom and is equal to
the number of independent variables which must
be specified in order to describe or fix the system;
C = the number of individual components taking
part in the reaction; P = the number of phases
present. In a system such as that represented by
Reaction 2.1, we may designate the temperature
and pressure (at equilibrium) as the two inde­
pendent variables. There are also two components,
M and H. In the a-phase region there is one solid
phase and one gas phase; thus, F = 2. Conse­
quently, both the pressure and temperature must
be specified to fix the system in this composition
region. In the “plateau” region, there are two solid
phases; the system is fixed when either the
temperature or pressure is specified.
The effect of increasing temperature is shown
by the higher temperature isotherms T2 and T3.
As the temperature rises, the miscibility gap tends
to narrow, accompanied by a consequent re­
duction in the “plateau” length. Eventually, at
som e critical (consolute) temperature, the
miscibility gap and the pressure plateau will
disappear and the a phase may convert continu­
ously into the hydride phase. More than one
hydride phase may occur in certain systems, in
which case a second and higher plateau may
appear. If so, the same considerations apply.
15
16
___V

1 H He
I A MB 1M B 3CB 3ZEB 3 M B

2 L iH B eH B C N 0 F Ne

3 NaH M gH2 VTTT A lH j Si P s Cl A

HA HA Y A 32XA YEA ------------------------- \ I B MB

VH C rH
4 KH C qH2 ScH 2 T iH 2 Mn Fe Co NiH CuH ZnH 2 6a Ge As Se Br Kr
vh 2 C rH 2

Hydrogen: Its Technology and Implications

y h 2 NbH
5 RbH S rH 2 Z rH 2 Mo Tc Ru Rh PdH Ag CdH2 In Sn Sb
YH, Te I Xe
N bH 2

6 C sH B aH 2 LoH , H fH 2 ToH W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra A c H2
7
? ?

C eH j P rH , NdH8 PmH2 Sm H 2 E u H2 GdH2 TbH 2 DyH2 HoH* TmHj YbH2 L u H2

m m

Pm Hj Sm H j GdH, TbH, D yH , H oH , Tm H , YbH , LuH ,

ThH 2 PoHj UH, NpH2 P u H2 AmH2 Cm BK Cf Es Fm Md Lr

No
Th^ N pH , PoH, AmH3 ? ? ? ? ? ? ? ?

FIGURE 2.1. Periodic chart showing occurrence of binary hydrides which exist as solids at room temperature. All, except underlined compounds, can
be prepared by the direct reaction of hydrogen. In cases where two distinct hydride phases are formed, both are noted. In order to prepare CrH and NiH
directly, very high pressures are required (>5000 atm).
Another random document with
no related content on Scribd:
272
Samar 5,040
13,054
Saranguani 36
93
Semerara 23
60
Siargao 134
347
Sibuyan 131
339
Siquijor 83
215
Sulu, or Jolo 241
624
Tablas 250
648
Ticao 94
243
Ybayat, or Ibayat 22
57
Ylin 24
62

GROUPS.

Alabat 76
197
Jomalig

Banton 44
114
Simara
 Romblon

Daram 41
106
Buad

Camotes group: 74
192
Ponson
Poro
Pasijan

Calaguas group:
Tinagua 19
49
Guintinua

Cuyos group: 28
73
Cuyos
Cugo
Agutaya
Hamipo
Bisukei

Laguan 23
60
Batag

Limbancauyan 184
477
Mesa, or Talajit
Maripipi
 Balupiri
Biliran

Lubang 53 163
Ambil
Golo

San Miguel 82 212

Batan
Cacraray
Rapurrapu

Tawi Tawi group: 183 414

Tawi Tawi
Tabulinga
Tandubato

Others of the
Tawi Tawi group. 54 140

Total measured 118,542 307,025

Estimated area of
unmeasured islands 1,000 2,500

Total area 119,542 309,615

{368}

Length of general shore line.

Name. Miles
Kilometers
 Bohol 161
259
Cebu 310
499
Jolo Archipelago 858
1,381
Kalamines 126
203
Leite 363
584
Luzon 2,144
3,450
Masbate 244
393
Mindanao 1,592
2,562
Mindoro 322
518
Negros 386
621
Palawan 644
1,036
Panay 377
607
Samar 412
663
Minor islands 3,505
5,641

Total 11,444
18,417
"The following [as to population] is a quotation from an
article by W. F. Wilcox, of the United States Census Bureau.
It is well to notice that the last official census was in 1887
and that the figures of that census, though probably
underestimating the population of the islands, are the ones
which, in default of better, we are obliged to take as final.
It is probable that these are an understatement of the true
population of the Philippines for several reasons, among which
is one not observed by Mr. Wilcox, and which is therefore
mentioned. It is, of course, only supposition, but is at least
suggestive. For every adult counted in the census the
officials were obliged to return a poll tax. Thus, for
instance, if 100,000 persons were counted 100,000 pesetas
would have to be returned to the treasury. It has therefore
been supposed that the officials counted, say, 150,000 and
returned only 100,000 pesetas and 100,000 names. Mr. Wilcox
says (American Statistical Association Publ., September,
1899): 'The population of the islands in 1872 was stated in a
letter to Nature (6:162), from Manila, by Dr. A. B. Meyer, who
gives the latest not yet published statistics as his
authority. The letter gives the population of nine islands, as
follows:

Luzon 4,467,111
Panay 1,052,586
Cebu 427,356
Leite 285,495
Bohol 283,515
Negros 255,873
Samar 250,062
Mindanao 191,802
Mindoro 70,926

"It also gives the population of each of the 43 provinces of

the islands. The population was not counted, but estimated.
The number who paid tribute was stated as 1,232,544. How this
 was ascertained we are not informed. The total population,
7,451,352, was approximated 'on the supposition that about the
sixth part of the whole has to pay tribute.' In reality this
population is 6.046 times the assigned tribute-paying
population. But Dr. Meyer adds: 'As there exist in all the
islands, even in Luzon, independent tribes and a large number
in Mindanao, the number of 7,451,352 gives no correct idea of
the real population of the Philippines. This is not known at
all and will not be known for a long time to come.'

"Since 1872 there have been actual enumerations of the

Philippines, but authorities differ as to the time when they
occurred and the detailed results. These enumerations were
usually confined to the subject and Catholic population, and
omitted the heathen, Mohammedan, and independent tribes. Four
reports of the entire population have been printed:

1. A report made by the religious orders in 1876 or 1877, in

which the nationalities and creeds of the population were
distinguished.

2. A manuscript report to Professor Blumentritt of the

enumeration made by the religious orders in December, 1879.

3. The official report of the civil census of December 31,

1877, contained in Reseña geog. y estad. de España, 1888, p.
1079.

4. The official report upon the census taken by the civil

officers December 31, 1887, and printed in the first volume of
Censo de la Poblacion de España, at Madrid, in 1891.

The first two may be compared, and tend somewhat to

corroborate each other, as follows:

1. Tribute-paying natives.
5,501,356
 2. Army
14,545
3. Navy
2,924
4. Religious officers (Geistlichkeit)
1,962
5. Civil officers
5,552
6. Other Spaniards
13,265

Total Spaniards
38,248

1876-77.
1879.
Total Catholics 5,539,604
5,777,522
Heathen and Mohammedan natives 602,853
632,640
Foreigners (In 1876 there were:
British, 176; German, 109;
Americans, 42; French, 30) 378
592
Chinese 30,797
39,054

Total 6,173,632
6,449,813
"The third enumeration reported 5,567,685 as the
tribute-paying population. To this number should be added the
estimated number of the independent tribes, 'Indios no
sometidos'; this according to the missionaries' count was
about 600,000, making a total of 6,167,685. Most experts agree
that this official report is untrustworthy and involves
serious omissions, but believe that the facts are so
imperfectly known that they are unable to correct it. One
author, del Pac, writing in 1882, started from the
missionaries' census of 1876-77, viz, 6,173,632, assumed that
this omitted as many as 600,000 members of independent tribes
and that the increase of 1876-1882 would be 740,000. In this
way he got 7,513,632. A second writer, Sanciano, estimated the
population in 1881 as 10,260,249. The missionaries made an
estimate of their own in 1885 which showed 9,529,841.
Seat of War in the Island of Luzon.

{369}

"The fourth enumeration of those mentioned above showed a

population of 5,985,123 in 1887, and the totals both for the
group as a whole and for the fifty odd provinces tend to
confirm and to be confirmed by the civil count of 1877. This
number, however, represents only the nominally Catholic or
tribute-paying population. To it must be added the Mohammedan
or heathen tribes set down by clerical authorities as about
600,000. Perhaps the highest authority in this field,
Professor Blumentritt, is confident that this number does not
include all the independent tribes, but only those in the
mountains who have a special arrangement freeing them from all
the dues of the subject tribes. On the whole, therefore, Prof.
H. Wagner is inclined to estimate these omissions of
independent or non-Christian tribes at about 1,000,000 and the
population of the group at about 7,000,000. This result is
indorsed by the latest German authority, Hübner's
Geographisch-Statistische Tabellen for 1898, which gives the
population as
5,985,124 + 1,000,000 = 6,985,124, as follows:

Spanish
Estimated number
census.
not counted.

Luzon and adjacent islands 3,443,000

150,000
Mindoro and Masbate 126,000
100,000
Visayas Archipelago 2,181,000
200,000
 Mindanao 209,000
400,000
Calamianes and Palawan 22,000
50,000
Jolo (Sulu) Islands 4,000
100,000

Total 5,985,000
1,000,000

"Personally I am disposed to suspect that this number,

although called by Professor Wagner an outside estimate, is
below rather than above the truth. In favor of this position
it may be urged that Professor Wagner's estimate makes no
allowance either for the natural increase of population,
1887-1898, or for the fact that the first careful census of
densely populated regions, like India and Japan, usually
reveals a larger population than had been previously
estimated. This analogy might reasonably be applied to Luzon
and the Visayas."

United States, 56th Congress, 1st Session,

Senate Document Number 171, pages 4-7.

PHILIPPINE ISLANDS:
The native inhabitants.

"The inhabitants of the Philippines belong to three sharply

distinct races—the Negrito race, the Indonesian race, and the
Malayan race. It is universally conceded that the Negritos of
to-day are the disappearing remnants of a people which once
populated the entire archipelago. They are, physically,
weaklings of low stature, with black skin, closely-curling
hair, flat noses, thick lips, and large, clumsy feet. In the
matter of intelligence they stand at or near the bottom of the
human series, and they are believed to be incapable of any
considerable degree of civilization or advancement. Centuries
ago they were driven from the coast regions into the wilder
interior portions of the islands by Malay invaders, and from
that day to this they have steadily lost ground in the
struggle for existence, until but a few scattered and
numerically insignificant groups of them remain. … It is
believed that not more than 25,000 of them exist in the entire
archipelago, and the race seems doomed to early extinction. …

"So far as is at present known, the Philippine tribes

belonging to the Indonesian race are confined to the great
island of Mindanao, the surface of which constitutes about
one-third of the total land area of the archipelago. … The
Philippine representatives of this race are physically
superior not only to the Negritos, but to the more numerous
Malayan peoples as well. They are tall and well developed,
with high foreheads, aquiline noses, wavy hair, and often with
abundant beards. The color of their skins is quite light. Many
of them are very clever and intelligent. None of the tribes
have been Christianized. Some of them have grown extremely
fierce and warlike as a result of their long struggle with
hostile Malayan peoples. Others, more happy in their
surroundings, are pacific and industrious.

"The great majority of the inhabitants of the Philippines are

of Malayan extraction, although the race is not found pure in
any of the islands, but is everywhere more or less modified
through intermarriage with Chinese, Indonesians, Negritos,
Arabs, and, to a limited extent, Spaniards and other
Europeans. The individuals belonging to these Malayan tribes
are of medium size, with straight black hair. As a rule the
men are beardless, and when they have a beard it is usually
straggling, and appears late in life. The skin is brown and
distinctly darker than that of the Indonesians, although very
much lighter than that of the Negritos. The nose is short and
frequently considerably flattened. The representatives of
these three races are divided into numerous tribes, which
 often differ very greatly in language, manners, customs, and
laws, as well as in degree of civilization. …

"Any estimate of the total population must manifestly depend

on the number of inhabitants assigned to the various wild
tribes, of which there are no less than 69. For the purposes
of this report the commission has adopted as the total figure
8,000,000, considering this a conservative estimate. Baranera,
whose figures are believed to be carefully prepared, places
the total at 9,000,000. The extent of territory occupied in
whole or in part by each of the more important civilized
tribes can be estimated with a greater degree of accuracy, and
is approximately as follows: Visayans (occupying 28,100 square
miles) 2,601,600; Tagalogs (15,380 sq. miles) 1,663,900;
Bicols (6,900 sq. miles) 518,100; Ilocanos (6,170 sq. miles)
441,700; Pangasinaus (1,950 sq. miles) 365,500; Pampangas
(1,950 sq. miles) 337,900; Moros (12,860 sq. miles) 268,000;
Cagayans(11,500 sq. miles) 166,300. All of these peoples,
although ignorant and illiterate, are possessed of a
considerable degree of civilization, and, with the exception
of the Mohammedan Moros, are Christianized."

Philippine Commission,
Report, January 31, 1900, volume 1, pages 11-15.

PHILIPPINE ISLANDS: A. D. 1896-1898.

The Katipunan and the rising against Spanish rule.
Appearance of Aguinaldo as a leader.
Dr. José Rizal.
The Treaty of Biac-na-bato.
Departure of Aguinaldo and his return with
the American forces.

The Philippine Islands, discovered in 1521 by Magellan (or

Maghallanes or Magalhaes), and occupied by the Spaniards in
1565, seems, for a long period, to have interested that people
more as a missionary than as a commercial field. Indeed, the
 doings of the church and of the religious orders, and the
acceptance of Roman teachings of Christianity by the greater
part of the native population, make up the essential history
of the Philippines until quite recent times. If the islands
had offered gold mines, or pearl fisheries, or spice forests
to their European discoverers, the story would certainly have
been different. As it was, the Spaniards were not moved to
much eagerness in exploiting such resources of commerce as
they found; and so, through fortunate circumstances, the
natives were made converts instead of slaves.
{370}
By missionaries, more than by soldiers, they were subdued; by
the church, more than by the Spanish state, they were ruled.
It is certain that there were great corruptions and
oppressions in the government, and it follows that a large
share of responsibility for them rests on those who controlled
the affairs of the church. For the past hundred years, at
least, the more spirited part of the native population has
been restive under the misrule and its burdens, and frequent
attempts at insurrection have been made. Such an outbreak in
1872 was suppressed and punished with a vengefulness, in
executions and banishment, which rankled ever afterwards in
the hearts of the people.

A secret society, called the "Katipunan," or League, was then

formed, which became a revolutionary organization, and from
which sprang the most serious of Filipino rebellions, in 1896.
The province of Cavite was the center of revolt, and it was
there that Emilio Aguinaldo, then the schoolmaster at Silan,
came into prominence as a leader. Mr. John Foreman, who was in
the Philippines at the time of the insurrection, states that
Aguinaldo was personally humane, but fearful atrocities were
committed in the first months of the rising by some of the
insurgents of his band. One captured priest, according to Mr.
Foreman's account, "was cut up piecemeal; another was
saturated with petroleum and set on fire; and a third was
bathed in oil and fried on a bamboo spit run through the
length of his body." The Spaniards, on their side, were
equally inhuman in their treatment of captured rebels and
"suspects." Says Mr. Foreman: "About 600 suspects were
confined in the dungeons of Fort Santiago at the mouth of the
Pasig River. Then occurred a frightful tragedy. The dungeons
are below water-mark at high tide; the river filtered in
through the crevices in the ancient masonry; thus twice a day
these unfortunates were up to their waists or necks in water,
according to the height of the men. The Spanish sergeant on
duty threw his rug over the only light and ventilating shaft,
and, in a couple of days, carts were seen by many citizens
carrying away the dead, calculated to number 70. Provincial
governors and parish priests seemed to regard it as a duty to
supply the capital with batches of 'suspects' from their
localities. In Vigan, where nothing had occurred, many of the
heads of the best families and monied men were arrested and
brought to Manila in a steamer. They were bound hand and foot,
and carried like packages of merchandise in the hold. I
happened to be on the quay when the steamer discharged her
living freight, with chains and hooks to haul up and swing out
the bodies like bales of hemp. …

"Thousands of peaceful natives were treated with a ferocity

which would have shocked all Europe. … Within three months of
the outbreak, hundreds of the richest natives and half-castes
in Manila were imprisoned for a few days and released
conditionally"—the condition being a payment of ransom,
sometimes said to be as high as $40,000. But General Blanco,
the then Governor-General, was not vigorous enough in his
measures to satisfy the all-powerful clerical party in the
islands, and he was replaced by General Polaveja, who received
large reinforcements from Spain, and who succeeded in breaking
the strength of the rebellion to a great extent. But the
character of Polaveja's administration is thus described by
Mr. Foreman: "Apart from the circumstances of legitimate
warfare, in which probably neither party was more merciful
than the other, he initiated a system of striking terror into
the non-combatant population by barbarous tortures and
wholesale executions. … Men were escorted to the prisons by
pure caprice and subjected to horrible maltreatment. Many of
them were liberated in the course of a few days, declared
innocent, but maimed for life and forever unable to get a
living. … The only apparent object in all this was to
disseminate broadcast living examples of Spanish vengeance."
The most notable victim at this period was Dr. José Rizal, a
physician, highly educated in Europe, distinguished as an
oculist, and the author of certain novels in which the
condition of things in his native country was set forth. On
his return to the Islands, Dr. Rizal incurred the enmity of
the friars by opposing them, and was pursued by their
hostility. From 1893 to 1896 he was kept in banishment,
closely watched, at a small town in the island of Mindanao.
Then he sought and obtained permission to go to Cuba in the
medical staff of the Spanish army; but, just as he arrived at
Manila, on his way to Spain, the insurrection of 1896 broke
out, and though he was suffered to depart, his enemies pursued
him with accusations of complicity in the rising and caused
him to be brought back. Says Mr. Foreman, who was an
eye-witness of what occurred: "Not a few of us who saw the
vessel leave wished him 'God speed.' But the clerical party
were eager for his extermination. … The lay authorities always
had to yield to the monks, and history herein repeated itself.
Dr. Rizal was cabled for to answer certain accusations, and so
on his landing in the Peninsula he was incarcerated in the
celebrated fortress of Montjuich (the scene of so many
horrors), pending his re-shipment by the returning steamer. He
reached Manila as a state prisoner in the Colon, isolated from
all but his jailors. It was materially impossible for him to
have taken any part in the rebellion, whatever his sympathies
may have been." Nevertheless, he was tried by court-martial
for sedition and rebellion, condemned and shot; and his memory
is cherished in the islands as that of a martyred patriot.
"The decree of execution was one of Polaveja's foulest acts."
 Having scotched but not killed the insurrection, Polaveja went
home, with broken health, in the spring of 1897, and was
succeeded by General Primo de Rivera, who, after some months
of continued warfare, opened negotiations with Aguinaldo, the
recognized leader of the revolt. The result was a treaty,
known as the "Pacto de Biac-na-bato, signed December 14. By
this treaty "the rebels undertook to deliver up their arms and
ammunition of all kinds to the Spaniards; to evacuate the
places held by them; to conclude an armistice for three years
for the application and development of the reforms to be
introduced by the other part, and not to conspire against
Spanish sovereignty in the Islands, nor aid or abet any
movement calculated to counteract the reforms.
{371}
Emilio Aguinaldo and 34 other leaders undertook to quit the
Philippine Islands, and not to return to them until so
authorised by the Spanish Government. On behalf of the Spanish
Government it was agreed to pay, through the medium of Pedro
A. Paterno, to the rebels the sum of $1,000,000, and to the
families who had sustained loss by reason of the war $700,000,
in instalments and conditionally,"—the condition being that no
renewal of rebellion or conspiracy occur. Aguinaldo and other
chiefs of the insurrection left the Islands, accordingly; but
they are said to have been utterly duped. One instalment, only
($400,000), of the promised money was ever paid; the promised
reforms were not carried out, and persecution of those who had
been in sympathy with the rising was renewed.

J. Foreman,
The Philippine Islands,
chapter 26 (New York: Charles Scribner's Sons).

"Aguinaldo and his associates went to Hongkong and Singapore.

A portion of the money, $400,000, was deposited in banks at
Hongkong, and a lawsuit soon arose between Aguinaldo and one
of his subordinate chiefs named Artacho, which is interesting
on account of the very honorable position taken by Aguinaldo.
 Artacho sued for a division of the money among the insurgents
according to rank. Aguinaldo claimed that the money was a
trust fund, and was to remain on deposit until it was seen
whether the Spaniards would carry out their promised reforms,
and if they failed to do so, it was to be used to defray the
expenses of a new insurrection. The suit was settled out of
court by paying Artacho $5,000. No steps have been taken to
introduce the reforms, more than 2,000 insurgents, who had
been deported to Fernando Po and other places, are still in
confinement, and Aguinaldo is now using the money to carry on
the operations of the present insurrection."

F. V. Greene,
Memorandum concerning the Situation in the Philippines,
August 30, 1898 (Treaty of Peace and Accompanying Papers:
55th Congress, 3d Session,
Senate Document Number 62, part 1, page 421.

PHILIPPINE ISLANDS: A. D. 1897.

Refusal of United States Government to negotiate
with the insurgent republic.

See (in this volume)

UNITED STATES OF AMERICA: A. D. 1897 (NOVEMBER).

PHILIPPINE ISLANDS: A. D. 1898 (April-May).

Circumstances in which Aguinaldo was brought to
Manila to co-operate with American forces.

See (in this volume)

UNITED STATES OF AMERICA:
A. D. 1898 (APRIL-MAY: PHILIPPINES).

PHILIPPINE ISLANDS: A. D. 1898 (April-July).

Destruction of the Spanish fleet in Manila Bay.
Blockade and siege of the city.
Co-operation of insurgents under Aguinaldo.
 See (in this volume)
UNITED STATES OF AMERICA: A. D. 1898 (APRIL-JULY).

PHILIPPINE ISLANDS: A. D. 1898 (May-August).

Conduct of English and German naval officers at Manila.

See (in this volume)

UNITED STATES OF AMERICA: A. D. 1898 (MAY-AUGUST).

PHILIPPINE ISLANDS: A. D. 1898 (July-August).

Correspondence between the American commander and Aguinaldo.

This is fully given (showing the relations between the

American and Filipino forces, before the capture of Manila),
in the general account of the Spanish-American War.

See (in this volume)

UNITED STATES OF AMERICA:
A. D. 1898 (JULY-AUGUST: PHILIPPINES).

PHILIPPINE ISLANDS: A. D. 1898 (July-September).

American capture of Manila.
Relations with the Filipino insurgents.
General Merritt's report.
Aguinaldo declared President of the Philippine Republic.

See (in this volume)

UNITED STATES OF AMERICA: A. D. 1898 (JULY-SEPTEMBER).

PHILIPPINE ISLANDS: A. D. 1898 (August).

Suspension of hostilities between the United States and Spain.
Manila held by the former pending the conclusion
of a treaty of peace.

See (in this volume)

UNITED STATES OF AMERICA: A. D. 1898 (JULY-DECEMBER).
PHILIPPINE ISLANDS: A. D. 1898 (August).
Losses of the American army during the war with Spain.

See (in this volume)

UNITED STATES OF AMERICA: A. D. 1900 (JUNE).

PHILIPPINE ISLANDS: A. D. 1898 (August-December).

The state of things following the occupation of Manila
by American forces.
Growing distrust and unfriendliness of the Tagalos.
General Otis's report.

Of the state of things which followed the departure of General

Merritt, August 30, General Otis, who succeeded him in
command, reported subsequently as follows:

"Until October 14 [1898], the United States troops in the

Philippines remained stationed at Manila and Cavite, as
provided in General Merritt's orders of August 23, with very
slight exceptions, Major-General Anderson retaining
supervision of the district of Cavite and Major-General
MacArthur of the troops stationed in Manila, the three
organizations composing the provost guard continuing, however,
under the control of Brigadier-General Hughes. They were most
bountifully supplied with subsistence and medicines, but light
clothing suited to the climate and facilities necessary for
occupying and messing in barracks were needed. These were soon
obtained through contract and purchase from the merchants of
Hongkong and Manila and by shipment from the United States.
The troops received tactical instructions daily, but the
weather was too hot for much physical exertion, and time hung
heavily upon them. They entertained the impression that the
Spanish war had terminated, and the volunteers appeared to
believe that they should be recalled to the United States at
once and regular troops sent out to perform the monotonous
garrison duties which were about to follow the victory of